Acyloxysteroids and process for producing same

Abstract

There is disclosed novel intermediates, i.e. acyloxysteroids, which are useful for the preparation of corticoids such as hydrocortisone and prednisolone, and a process for producing the same.

What is claimed is: 
     
       1. A diiodosteroid of formula (Ia): ##STR16## wherein the dotted lines in the rings independently represent a single or double bond and A represents an acyloxy group. 
     
     
       2. A process for producing a diiodosteroid of formula (Ia): ##STR17## wherein the dotted lines in the rings independently represent a single or double bond and A represents an acyloxy group, which comprises: reacting an iodizing agent selected from the group consisting of N-iodoimide, N-iodoamide and the combination of an oxidizing agent and iodine capable of releasing positive iodine atoms with a 17β-ethynyl-17α-acyloxysteroid of formula (II): ##STR18## wherein the dotted lines and A are as defined in formula (Ia). 
     
     
       3. The process of claim 2, wherein said iodizing agent is an N-iodoimide or an N-iodoamide. 
     
     
       4. The process of claim 2, wherein said iodizing agent comprises an oxidizing agent and iodine. 
     
     
       5. A process for producing a monoiodosteroid of formula (Ib): ##STR19## wherein the dotted lines in the rings independently represent a single or double bond and A represents an acyloxy group, which comprises: contacting a diiodosteroid of formula (Ia): ##STR20## wherein the dotted lines and A are as defined in formula (Ib), with an organic solvent selected from the group consisting of methyl ketones and amines. 
     
     
       6. The process of claim 5, wherein said diiodosteroid is contacted in said organic solvent with a base. 
     
     
       7. The process for producing a monoiodosteroid of formula (Ib): ##STR21## wherein the dotted lines in the rings independently represent a single or double bond and A represents an acyloxy group, which comprises: reducing a diiodosteroid of formula (Ia): ##STR22## wherein the dotted line and A are as defined in formula (Ib), with a dithionite. 
     
     
       8. A dibromosteroid of formula (Ic): ##STR23## wherein the dotted lines in the rings independently represent a single or double bond and A represents an acyloxy group. 
     
     
       9. A process for producing a dibromosteroid of formula (Ic): ##STR24## wherein the dotted lines in the rings independently represent a single or double bond and A represents an acyloxy group, which comprises: reacting N-bromoimide or N-bromoamide with a 17β-ethynyl-17α-acyloxysteroid of formula (II): ##STR25## wherein the dotted lines and A are as defined in formula (Ic). 
     
     
       10. A process for producing a monobromosteroid of formula (Id): ##STR26## wherein the dotted lines in the rings independently represent a single or double bond and A represents an acyloxy group, which comprises: reacting a dibromosteroid of formula (Ic): ##STR27## wherein the dotted lines and A are as defined in formula (Id), with a trialkyl phosphite or a triaryl phosphite.